Investigations of the performance of quartz single aliquot DE determination procedures

Over the past few years a variety of equivalent dose (D_E) determination techniques for quartz, which are truly single aliquot-based, have been proposed. Such methods avoid the need for inter-aliquot normalisation, and provide considerable improvements in the precision of equivalent dose (D_E) estimates. Much of the research leading to these developments have been based on detailed investigations of a few samples, primarily from Australia. All ’protocols’ developed have performed impressively. It is necessary, however, to verify the consistency of the single aliquot D_E determination methods on a wide range of samples before they can be considered as prescribed or standard. We have analysed approximately 100 samples from a range of sedimentary environments and geological provinces in an attempt to confirm the robustness of the single aliquot techniques. Up to 65% of samples measured in our laboratory were not suited to analysis via application of single aliquot additive dose (SAAD) procedures. This relates to a range of factors, including lack of sample sensitivity and dose dependent sensitivity changes. Furthermore, we have observed some problems in dating young sediments using single aliquot regeneration (SAR) methods. Critically, we observe that sample to sample variability on quartz luminescence (thermally- and optically-stimulated) behaviour is considerable, and many samples are found to exhibit behaviour which contrasts greatly from that described in recent phenomenological studies.     

Paper II: The interpretation of measurement-time-dependent single-aliquot equivalent-dose estimates using predictions from a simple empirical model

Narrow spectrum (blue-green) laboratory partial bleaching of aliquots of natural sedimentary quartz has been shown to have a significant effect on equivalent dose (measured using a single aliquot procedure) calculated as a function of measurement time (D_e(t)). A simple model, based on empirical data, is presented in which the effects of partial bleaching on D_e(t) are predicted, taking into account the influences of pre- and post-burial doses. The model is applied to the case of heterogeneous populations of partially bleached single grains with various ranges of residual doses. Modelling shows that under realistic conditions, D_e histogram plots are unable to distinguish between samples having age overestimates and those with correct ages, whereas the proposed D_e–Z plot is able to make this distinction. Furthermore, modelling shows that D_e–Z plots can identify sub-populations of grains/aliquots that show most evidence of full bleaching, which can then be used to estimate a correct mean D_e value.     

Paper I: The use of measurement-time dependent single-aliquot equivalent-dose estimates from quartz in the identification of incomplete signal resetting

The identification of incomplete signal re-setting of optically stimulated luminescence signals in sedimentary quartz is a vitally important step in the continued improvement of optical dating. It is shown that narrow spectrum (blue-green) laboratory partial bleaching of aliquots of natural sedimentary quartz has a significant effect on equivalent dose (measured using a single aliquot procedure) calculated as a function of measurement time (D_e(t)). The blue-green stimulation spectrum mimics that found underwater and the results suggest that incomplete re-setting of waterlain sediments may be possible using the D_e(t) method.     

A systematic study of the radioluminescence properties of single feldspar grains

Spectral radioluminescence properties of a large number of single grains were measured. The main emission in K-feldspar grains occurs in the infrared range with the same dose characteristic as shown by multi-grain samples. For plagioclases, large differences in spectral radioluminescence between single-grains and multi-grain aliquots were detected. Differences in the saturation of the dose characteristics of the individual emissions have been observed. Consequences for dating application are discussed.     

Natural IRSL intensities and apparent luminescence ages of single feldspar grains extracted from partially bleached sediments

The single aliquot technique has been applied to single grains of K-feldspar extracted from a well-dated late-glacial marine sediment sample for which standard luminescence dating yielded ages that were in excess of the expected age. Natural infrared-stimulated luminescence (IRSL) intensities as well as single grain palaeodoses show a wide range of values. Most of the bright grains yield equivalent doses largely in excess of the expected palaeodose, considering the depositional age of the sample. The luminescence emitted by the brightest grains would dominate the signal emitted from aliquots containing many grains. This explains the overestimation of ages obtained using standard luminescence techniques for the sample investigated. Palaeodoses obtained from grains that exhibit low IRSL intensities are close to the expected dose. However, the age derived from these grains is lower than the expected age. Anomalous fading is believed to be the main cause for the age underestimation. This study is the first demonstration of the feasibility of dating a sedimentary event using the luminescence of a single mineral grain.     

Circumventing possible inaccuracies of the single aliquot regeneration method for the optical dating of quartz

A simple method of assessing the reliability of the single aliquot regeneration method is presented, based on the repeated measurement of identical regeneration doses. It is shown that for the majority of the samples measured the requirement of a constant repeat point in each cycle is not met. The ability to maintain a constant repeat point is shown to be dependent upon preheating conditions, the requirements for which were found to vary at both inter-sample and inter-aliquot levels. The expected effect on estimated values of D_e is calculated and shown to be significant. Three possible means of circumventing these inaccuracies are presented: (i) adjustment of the measurement procedure (specifically the preheat conditions); (ii) modelling and correcting for the effect, and (iii) stabilising the response prior to construction of the regenerated growth curve. It is suggested that much of the variation in D_e observed between individual aliquots and between individual grains from well-bleached sediments may possibly be attributed to differences in preheating requirements, and that such differences may also account for some of the spread in D_e for partially bleached sediments.     

Luminescence sensitivity changes of polymineral fine grains during IRSL and [post-IR] OSL measurements

Sensitivity changes during measurement sequences of infra-red-stimulated luminescence (IRSL) and post-IR optically stimulated luminescence (OSL) are presented for a sample of loess from northwestern China. Together with a dose recovery experiment, the results are used to investigate the ratio of 2.4 found for the D_e values (for IRSL and [post-IR] OSL) obtained when using a single-aliquot regenerative-dose (SAR) protocol in which both D_e values are obtained in a single sequence of measurements. Responses to test doses for both the IRSL and [post-IR] OSL show progressive luminescence sensitivity changes with repeated measurement cycles, with a slight dose dependence for the IRSL. In addition, five modified SAR procedures were used, varying preheats, filter combinations and method of measuring the luminescence signal. The D_e values for all IRSL measurements were at least 50% greater than those for the [post-IR] OSL signal. A modified SAR sequence was also applied in which 0.1 s stimulations (using both IR and blue light sources) were made between all sample treatments. A lack of consistency in the measured luminescence sensitivity of the natural IRSL signal suggests that the [post-IR] OSL signal provides the more reliable value of D_e.     

Quartz from southern Africa: sensitivity changes as a result of thermal pretreatment

Sensitivity changes are known to occur in quartz during luminescence measurement procedures. Accurate single-aliquot equivalent dose (D_e) evaluations can be made only if the experimental procedure applied causes no sensitivity change, or can correct for it. The quartz single-aliquot regenerative-dose (SAR) protocol developed by Murray and Wintle (Murray, A.S., Wintle, A.G., 2000. Luminescence dating of quartz using an improved single-aliquot regenerative-close protocol. Radiation Measurements 32, 57–73) incorporates a sensitivity correction procedure that was developed using measurements made on a single sample from Australia. This paper presents experimental data designed to test the applicability of this correction procedure to quartz extracted from two southern African sediments. The results indicate that accurate corrections are made using this protocol irrespective of the direction and magnitude of the sensitivity change. The implications for routine D_e evaluation are discussed.     

Particle counting and numerical models: Effect of instrumental size resolution and particle shapes on optical cross-sections

The effect of instrumental size resolution measurements on numerical calculations of optical cross-sections is investigated. The particle counting instruments considered are a FSSP-300, a large scattering angle probe instrument similar to a ASASP-X, and, an aerodynamical system ELPI instrument. The scattering and hemispheric backscattering cross-sections, C_sca and C_bk, are calculated on the basis that the full width of the instrumental size bin should be considered in modeling. An average process is applied on these quantities over the full size bin of the instrument; they are then compared to their usual estimation on the single mean diameter D_p per channel. The effect of particle shape is investigated with ellipsoids and spheres. Results show sensitivity of the optical cross-sections to the shape of the particles as well as position of the mean geometrical diameter D_p of the channels within the interferences modes of the scattering efficiencies. The value of the width of the size bins, d log D, of each channel is crucial in the results. This comparison gives a useful estimation of error important in optical particle counting instruments based on inversion process of optical quantities. In addition, accuracy of size distribution measurements is found not to be representative of accuracy in the calculations of optical cross-sections.     

Some aspects of single-grain luminescence dating

Single-grain methods of luminescence dating have been developed in order to circumvent problems of variability among aliquots of the sample being dated. Sufficient single grains must be separated in order to make an appropriate interpretation of the variability among such grains. We describe an automated apparatus for sorting grains for routine age determinations by green light stimulation. The sorted grains are then available for study of their collective luminescence physics characteristics. Examples are given of statistical frequency functions of grain brightness obtained with the apparatus and their interpretation. These frequency functions are lognormal or similar, covering up to four orders of magnitude, with consequent implications for luminescence dating application.     

回波间隔对核磁共振表观孔隙度的影响及矫正方法

本文对具有特定横向弛豫时间（T₂）的硫酸铜溶液进行了多回波间隔（T_E）的核磁共振（NMR）实验,并利用数值模拟对32组具有不同弛豫分量的模型进行了变T_E模拟实验,定量研究了T_E对致密油气、页岩气等低孔低渗储层NMR孔隙度的影响规律.实验结果表明,随着T_E的增大,各T₂弛豫组分NMR孔隙度先维持在100%左右,然后迅速衰减,当T_E增加到一定数值时,趋近于0;不同T₂弛豫组分NMR孔隙度开始迅速衰减及最后变为0的T_E值存在显著差异.根据不同T₂弛豫组分NMR孔隙度与T_E的关系,将整个NMR测量分为无损测量区、快速衰减区、无效参数区和仪器盲区4个区域.对特定弛豫组分而言,在快速衰减区弛豫组分损失量与T_E呈对数关系,本文还给出了该区域NMR孔隙度的校正公式及方法.     

Electron–hole recombination luminescence in LiYF4:U single crystal

Photoluminescence (PL), photostimulated luminescence (PSL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) studies were carried out on LiYF₄:U⁴⁺ and pure LiYF₄ crystals. The PL and EPR investigations have identified the presence of Eu³⁺, Tb³⁺ and Gd³⁺ ions in both of these crystals possibly due to their existence in the starting materials. The luminescence observed during afterglow, PSL and TSL revealed that emission occurs at wavelength positions 382, 413, 437 and 544 nm, which are characteristic of Tb³⁺ ions. The present investigations using PSL and TSL in combination with PL studies before and after gamma irradiation have revealed that selective energy transfer to Tb³⁺ ions occurs during electron–hole recombination processes like PSL and TSL. Even though other luminescent ions (U⁴⁺ and Eu³⁺) are present in the system and U⁴⁺/U³⁺ ions are participating in electron capture/release processes, the selective energy transfer results in Tb³⁺ ions acting as luminescence centers.     

Empirical insights into multi-grain averaging effects from ‘pseudo’ single-grain OSL measurements

In this study we assess the signatures of multi-grain averaging effects for a series of sedimentary samples taken from the archaeological site of Hotel California, Atapuerca, Spain. We focus on the special case of equivalent dose (D_e) measurements made on single-grain discs that contain more than one quartz grain in each of the individual grain-hole positions with the aims of (i) providing insight into the nature and extent of averaging effects in very small multi-grain aliquots of sedimentary quartz, and (ii) assessing the suitability of ‘pseudo’ single-grain D_e measurements for this particular dating application. Pseudo single-grain OSL measurements made on standard discs loaded with 90–100 μm grains (equivalent to ～30 grains per hole) yield significantly different D_e distribution characteristics and finite mixture model (FMM) burial dose estimates compared with single-grain OSL measurements. Grains with aberrant luminescence behaviours, which are routinely rejected during single-grain analysis, exert strong averaging effects on the pseudo single-grain and multi-grain aliquot D_e distributions. Grain-hole averaging effects arising from pseudo single-grain measurements also give rise to ‘phantom’ dose components and are apt to provide bias assessments of quartz signal characteristics and grain type classifications. Though this is a site-specific study, it serves as a cautionary note for interpretations of other pseudo single-grain OSL and D_e datasets – particularly those obtained from measurements of discs containing several tens of grains per hole and those derived from complex depositional environments. The use of custom single-grain discs drilled with smaller sized grain holes is recommended as a means of limiting grain-hole averaging effects when dealing with very fine (<180 μm) sediments.     

Radiation defects in Ce-activated fluorobromozirconate glass-ceramic X-ray storage phosphors

We report on a photostimulated luminescence (PSL) effect in Ce-doped fluorobromozirconate glasses. Small hexagonal or orthorhombic BaBr₂ crystallites are formed in the glass upon annealing. The PSL shows a (381,415) nm doublet which is due to the 5d–4f luminescence of Ce³⁺ in the orthorhombic BaBr₂ crystallites embedded in the glass matrix. The stimulation band of the PSL peaking at 580 nm is probably due to perturbed F centres in the crystallites. After X-irradiation the magnetic circular dichroism of the optical absorption showed a broad band in the spectral range between 440 and 800 nm, having a derivative-like line shape centred at about 600 nm. The spectrum consists of two overlapping bands: one, derivative-like, belongs probably to F-centres, whereas the second band, superimposed on the low-energy region of the F-centre band, is due to a hole centre.     

Photoluminescence and photostimulated luminescence in the X-ray storage phosphor BaBr2 doped with cerium

In orthorhombic BaBr₂ : Ce³⁺ two kinds of luminescence bands at room temperature have been attributed to charge-compensated Ce³⁺ centres. One type was associated with potassium (or some other monovalent cation) on a neighbouring Ba site and another one associated with an unidentified defect. A third kind of emission, observed only as low temperature photoluminescence (PL), is ascribed to isolated Ce³⁺ ions. The charge-compensated Ce³⁺ complexes are active both in PL and photostimulated luminescence (PSL) following X-ray irradiation. The PSL is nearly as efficient as in the case of the commercially used X-ray storage phosphor BaFBr:Eu²⁺. The X-ray induced electrons are trapped in F-type centres whose band position is characteristic for the nearby Ce complex. As shown by the fingerprint character of the PSL itself, the hole partner in the recombination is also associated or identical with the same Ce complex.     

Tm3+掺杂SrAl2O4:Eu2+的光激励和热释光性能

通过高温固相法制备出Sr_{0.98-xAl2O4:0.02Eu²⁺,xTm³⁺(x=0,0.01,0.02,0.03,0.04,0.05)系列样品,并对其光激励和热释光性能进行了研究。在SrAl2O4:Eu²⁺原有陷阱能级结构的基础上,通过Tm³⁺的掺杂引入了更深的陷阱TB,并增加原有陷阱TA浓度,进而优化了材料的光存储容量及光激励特性。对比研究了系列样品的初始光激励发光强度和热释光强度随着Tm³⁺掺杂量的变化规律,证实陷阱TB为光激励发光提供了有效俘获中心。当Tm³⁺的掺杂摩尔分数x=0.03时,材料中的陷阱TB的浓度达到最高值,同时光激励发光强度最大。对比Tm³⁺共掺前后热释光图谱,通过Chen's半宽法计算出了引入陷阱TB的陷阱深度。实验结果证实材料中TB的浓度对其光激励发光性能起着决定性的作用。在980 nm激发下,由深陷阱TB释放出来的电子可以再次被浅陷阱TA俘获,这种浅陷阱TA的再俘获效应在光激励发光过程中表现为光激励余辉现象。}     

Cr3+掺杂的Ca3Al2Ge3O12石榴石的光谱性质

在此报告钙铝锗石榴石Ca₃Al₂Ge₃O₁₂中Cr³⁺离子的光谱特性,依据不同浓度的样品在不同温度下发射光谱的实验结果,分析了不等价Cr³⁺发光中心零声子线R₁,R₂的位置变化情况。通过对Cr³⁺吸收和发射光谱的分析,估算了Cr³⁺所处格位的晶场强度参数Dq和Racah参数,同时,对低温下Cr³⁺R线边带振动光谱的精细结构的起因进行了分析和指认。在室温和低温下测得Cr³⁺的⁴T₂→⁴A₂和²E→⁴A₂能级跃迁的荧光衰减为单指数规律。     

三角对称晶场下d8电子组态的EPR参量的普遍公式及其应用

本文考虑到d⁸电子组态中所有自旋三重态和自旋单态对基态的影响,用高阶微扰法导出了d⁸电子组态在三角对称晶场下光谱和基态EPR普遍公式。发现在三角对称晶场下,d⁸电子组态离子的g_⊥ > g_‖或g_⊥ < g_‖和D > 0或D < 0是以立方对称晶场为界,晶体中顺磁离子的配体沿C₃轴伸长或压缩所致。利用所得公式计算了NiCl₂和NiSiF₆·6H₂O晶体的EPR参量,其结果与实验吻合较好。     

Eu^2＋：BaFCl光激励发光衰减的研究

制备了系列材料Ｅｕ＾２＋：ＢａＦＣｌ，测量了其光激励发光的衰减曲线，基于隧穿模型，建立了描述隧穿过程的数学模型，得出了光激励发光衰减规律，并将结果与实验进行了比较。     

A new irradiated quartz for beta source calibration

For luminescence dating to be an accurate absolute dating technique it is very important that we are able to deliver absolutely known radiation doses in the laboratory. This is normally done using a radiation source (alpha, beta, X-ray) calibrated against an absolutely known reference source. Many laboratories have used the various different batches of Risø calibration quartz for the calibration of beta and X-ray sources, but these have been largely undescribed. Here we describe in detail the preparation and luminescence characteristics of a new quartz standard, based on a North Sea beach sand collected from south-western Denmark (Rømø). Two grain sizes (4–11 μm and 180–250 μm) have been examined in detail. These were pre-treated (annealed, dosed and annealed again) to sensitise and stabilise the luminescence signals before being given an absolutely known gamma dose from a point ¹³⁷Cs source in scatter-free geometry. The luminescence characteristics are described; the very intense blue-light stimulated signal is dominated by the fast OSL component and the IR-stimulated signal is negligible. The material is shown to be suitable for measurement using SAR, and the dose recovery ratio is indistinguishable from unity with a standard deviation of <2% for multi-grain aliquots. The material is also shown to be suitable for single-grain calibration, with >80% of the grains giving a useful signal. Although there is an unexplained dispersion in our calibration data of ∼3% (which we cannot attribute to instrument variability), we nevertheless conclude that this material is very suitable for transferring absolute known doses from a standardised gamma source to in-built irradiation sources.